U.S. patent application number 14/964585 was filed with the patent office on 2016-12-01 for composite carbon material and method of preparing the same.
The applicant listed for this patent is National Taiwan University of Science and Technology. Invention is credited to Wei-Hung Chiang, Yen-Sheng Li.
Application Number | 20160351287 14/964585 |
Document ID | / |
Family ID | 57397649 |
Filed Date | 2016-12-01 |
United States Patent
Application |
20160351287 |
Kind Code |
A1 |
Chiang; Wei-Hung ; et
al. |
December 1, 2016 |
COMPOSITE CARBON MATERIAL AND METHOD OF PREPARING THE SAME
Abstract
Provided is a composite carbon material including a substrate
and a graphene oxide. The graphene oxide accounts for about 5 wt %
to 60 wt % based on a total weight of the substrate and the
graphene oxide. A method of preparing a composite carbon material
is further provided. The prepared composite carbon material has
excellent hydrophilic property, flexibility, electrical
conductivity and dispersity.
Inventors: |
Chiang; Wei-Hung; (Taipei,
TW) ; Li; Yen-Sheng; (Taipei, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
National Taiwan University of Science and Technology |
Taipei |
|
TW |
|
|
Family ID: |
57397649 |
Appl. No.: |
14/964585 |
Filed: |
December 10, 2015 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01B 1/08 20130101 |
International
Class: |
H01B 1/08 20060101
H01B001/08 |
Foreign Application Data
Date |
Code |
Application Number |
May 29, 2015 |
TW |
104117456 |
Claims
1. A composite carbon material, comprising: a substrate; and a
graphene oxide, wherein the graphene oxide accounts for 5 wt % to
60 wt % based on a total weight of the substrate and the graphene
oxide.
2. The composite carbon material according to claim 1, wherein the
substrate comprises an oxidized, doped, or undoped carbon nanotube,
a doped or undoped graphite, a doped or undoped graphene, a
molybdenum dioxide, or a combination thereof, and a doping element
comprises sulfur, phosphorus, boron, nitrogen or a combination
thereof.
3. The composite carbon material according to claim 1, wherein the
substrate comprises a one-dimensional conductor, a two-dimensional
conductor, a three-dimensional conductor, or a combination
thereof
4. The composite carbon material according to claim 1, wherein the
graphene oxide comprises a graphene oxide having a one-dimensional
conducting direction, a graphene oxide having a two-dimensional
conducting direction, or a combination thereof
5. The composite carbon material according to claim 1, wherein the
composite carbon material is a flexible composite material having a
conductive network structure.
6. A method of preparing a composite carbon material, comprising:
uniformly mixing a substrate and a graphene oxide in a solvent,
wherein the graphene oxide accounts for 5 wt % to 60 wt % based on
a total weight of the substrate and the graphene oxide.
7. The method of preparing the composite carbon material according
to claim 6, wherein the step of removing the solvent comprises
performing a suction filtration, a natural drying, or a baking.
8. The method of preparing the composite carbon material according
to claim 6, wherein the step of uniformly mixing the substrate and
the graphene oxide in the solvent does not require addition of a
surfactant.
9. The method of preparing the composite carbon material according
to claim 6, wherein a method of preparing the graphene oxide
comprises: embedding a nitrate, a sulfate, or a combination thereof
between layers of a carbon material or between adjacent carbon
materials; and adding an oxidizing agent to oxidize the carbon
material.
10. The method of preparing the composite carbon material according
to claim 6, wherein the substrate comprises an oxidized, doped or
undoped carbon nanotube, a doped or undoped graphite, a doped or
undoped graphene, a molybdenum dioxide, or a combination thereof, a
doping element comprises sulfur, phosphorus, boron, nitrogen or a
combination thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the priority benefit of Taiwan
patent application serial no. 104117456, filed on May 29, 2015. The
entirety of the above-mentioned patent application is hereby
incorporated by reference herein and made a part of the
specification.
BACKGROUND OF THE INVENTION
[0002] Field of the Invention
[0003] The invention relates to a composite material and a method
of preparing the same, and more particularly relates to a composite
carbon material and a method of preparing the same.
[0004] Description of Related Art
[0005] Current flexible electronic components or wearable
electronic components require transparent and flexible electrodes.
However, the existing indium tin oxide (ITO) has poor dispersity
due to a hydrophobic nature. Thus, conductive components made by
ITO have poor flexibility and break easily, resulting in poor
electrical conductivity.
[0006] Furthermore, conventional conductive carbon materials are
hydrophobic and unable to be effectively dispersed, and thus,
addition of a surfactant or a solvent is required to increase the
dispersity. However, such surfactant or solvent is usually
non-conductive, resulting in a decrease in electrical conductivity
of the original carbon materials. When being applied, the
surfactant or solvent is required to be further purified, which not
only results in complicated steps but is also very environmentally
unfriendly.
SUMMARY OF THE INVENTION
[0007] Accordingly, the invention provides a composite carbon
material and a method of preparing the same, wherein a graphene
oxide replaces a conventional surfactant to achieve effective
dispersion and facilitate electrical conductive function.
[0008] The invention provides a composite carbon material including
a substrate and a graphene oxide. The graphene oxide accounts for
about 5 wt % to 60 wt % based on a total weight of the substrate
and the graphene oxide.
[0009] In an embodiment of the invention, the substrate includes an
oxidized, doped or undoped carbon nanotube, a doped or undoped
graphite, a doped or undoped graphene, a molybdenum dioxide, or a
combination thereof, a doping element includes sulfur, phosphorus,
boron, nitrogen or a combination thereof
[0010] In an embodiment of the invention, the substrate includes a
one-dimensional conductor, a two-dimensional conductor, a
three-dimensional conductor, or a combination thereof
[0011] In an embodiment of the invention, the graphene oxide
includes a graphene oxide having a one-dimensional conducting
direction, a graphene oxide having a two-dimensional conducting
direction, or a combination thereof.
[0012] In an embodiment of the invention, the composite carbon
material is a flexible composite material having a conductive
network structure.
[0013] The invention also provides a method of preparing a
composite carbon material. A substrate and a graphene oxide are
uniformly mixed in a solvent, wherein the graphene oxide accounts
for about 5 wt % to 60 wt % based on a total weight of the
substrate and the graphene oxide. Next, the solvent is removed.
[0014] In an embodiment of the invention, the step of removing the
solvent includes performing a suction filtration, a natural drying,
or a baking.
[0015] In an embodiment of the invention, the step of uniformly
mixing the substrate and the graphene oxide in the solvent does not
require addition of a surfactant.
[0016] In an embodiment of the invention, a method of preparing the
graphene oxide includes: embedding a nitrate, a sulfate, or a
combination thereof between layers of a carbon material or between
adjacent carbon materials, and adding an oxidizing agent to oxidize
the carbon material.
[0017] In an embodiment of the invention, the substrate includes an
oxidized, doped or undoped carbon nanotube, a doped or undoped
graphite, a doped or undoped graphene, a molybdenum dioxide, or a
combination thereof, a doping element includes sulfur, phosphorus,
boron, nitrogen or a combination thereof.
[0018] In view of the above, in the invention, a graphene oxide
instead of a conventional surfactant is added into a substrate. The
graphene oxide is rich in oxygen-containing functional groups, has
excellent dispersion property, and forms a dense conductive network
with the substrate. The graphene oxide of the invention not only
facilitates dispersion of the carbon-containing substrate, but the
graphene oxide itself also has electrical conductive property and
can be used without requiring further purification. Therefore, the
composite carbon material including the substrate and the graphene
oxide has better electrical conductivity and dispersity than those
of the original substrate.
[0019] To make the above and other features and advantages of the
invention more comprehensible, embodiments accompanied with
drawings are described in detail as follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The accompanying drawings are included to provide a further
understanding of the invention, and are incorporated in and
constitute a part of this specification. The drawings illustrate
exemplary embodiments of the invention and, together with the
description, serve to explain the principles of the invention.
[0021] FIG. 1 is a perspective schematic diagram of a composite
carbon material according to an embodiment of the invention.
[0022] FIG. 2 is a schematic diagram of a method of preparing a
composite carbon material according to an embodiment of the
invention.
[0023] FIGS. 3(a), 3(c) and 3(e) are images of a conventional
conductive thin film of
[0024] Comparative Example 1, wherein the scale bar of FIG. 3(c) is
100 .mu.m, and the scale bar of FIG. 3(e) is 500 .mu.m.
[0025] FIGS. 3(b), 3(d) and 3(f) are images of a conductive thin
film of Example 1 of the invention, wherein the scale bar of FIG.
3(d) is 100 .mu.m, and the scale bar of FIG. 3(f) is 500 .mu.m.
[0026] FIG. 4(a) is a resistance value distribution of a
conventional conductive thin film of Comparative Example 1.
[0027] FIG. 4(b) is a resistance value distribution of a conductive
thin film of Example 1 of the invention.
[0028] FIG. 5 is a graph illustrating a relationship between a
resistance value and a graphene oxide content in a composite carbon
material of Example 2 of the invention.
[0029] FIG. 6 is a graph illustrating a relationship between a
resistance value and a graphene oxide content in a composite carbon
material of Example 3 of the invention.
[0030] FIG. 7 is a graph illustrating a relationship between a
resistance value and a graphene oxide content in a composite carbon
material of Example 4 of the invention.
DESCRIPTION OF THE EMBODIMENTS
[0031] The invention provides a simple method of preparing a
composite carbon material, and the prepared composite carbon
material has excellent hydrophilic property, flexibility,
electrical conductivity and dispersity.
[0032] Herein, although materials have spatial three-dimensional
structures, based on conducting directions thereof, the materials
can be divided into "one-dimensional conductors (1-D conductors)",
"two-dimensional conductors (2-D conductors)", and
"three-dimensional conductors (3-D conductors)". When the material
is conductive only in a particular direction, namely, the
conducting direction thereof is one-dimensional, such material is
called a "one-dimensional conductor". When the material is
conductive only in a particular plane, namely, the conducting
direction thereof is two-dimensional, such material is called a
"two-dimensional conductor". When the conducting direction thereof
is three-dimensional, such material is called a "three-dimensional
conductor".
[0033] FIG. 1 is a perspective schematic diagram of a composite
carbon material according to an embodiment of the invention.
[0034] As shown in FIG. 1, the composite carbon material 1 of the
invention includes a substrate 10 and a graphene oxide 20. In an
embodiment, the substrate 10 includes an oxidized, doped or undoped
carbon nanotube, a doped or undoped graphite, a doped or undoped
graphene, a molybdenum dioxide, or a combination thereof. The
doping element for doping the substrate includes sulfur,
phosphorus, boron, nitrogen or a combination thereof. The material
of the substrate 10 can also be categorized based on the dimension
of the conducting direction/dimension thereof. More specifically,
the substrate 10 includes a one-dimensional conductor, a
two-dimensional conductor, a three-dimensional conductor, or a
combination thereof, and the respective shapes and types are as
shown in Table 1, but the invention is not limited thereto.
TABLE-US-00001 TABLE 1 Types of substrate Substrate Shape Type 1-D
strip oxidized, doped or undoped single-walled conductor carbon
nanotube, oxidized, doped or undoped double-walled carbon nanotube,
oxidized, doped or undoped multi-walled carbon nanotube or a
combination thereof, doped or undoped graphene nanoribbon or a
combination thereof 2-D sheet doped or undoped graphene, molybdenum
conductor dioxide, or a combination thereof 3-D laminate doped or
undoped graphite conductor
[0035] The conducting direction of the graphene oxide 20 can be
one-dimensional or two-dimensional. Herein, a graphene oxide having
a one-dimensional conducting direction is referred to as a
"one-dimensional graphene oxide (1-D graphene oxide)," and a
graphene oxide having a two-dimensional conducting direction is
referred to as a "two-dimensional graphene oxide (2-D graphene
oxide)". In an embodiment, the graphene oxide 20 includes a
one-dimensional graphene oxide, a two-dimensional graphene oxide,
or a combination thereof
[0036] In the graphene oxide 20, based on the total number of atoms
of carbon and oxygen, carbon accounts for about 0.1 at % to 99.9 at
% , such as 5 at % to 40 at %, 5 at % to 30 at %, 5 at % to 20 at %
or 5 at % to 15 at %. In an embodiment, the content of oxygen of
the graphene oxide 20 is about 5 at %, 10 at %, 15 at %, 20 at %,
25 at %, 30at %, 35 at %, 40 at %, or any numerical value between
any two endpoints above. With an increase in the content of oxygen,
the resistance value of the graphene oxide is increased, but the
dispersity is improved.
[0037] The composite carbon material 1 of the invention is a
flexible composite material having a conductive network structure.
As shown in FIG. 1, the substrate 10 and the graphene oxide 20 are
interconnected and/or entangled to form a network structure and/or
a web structure. In an embodiment, the substrate 10 and the
graphene oxide 20 are physically mixed without chemical bonding
between each other.
[0038] It is noted that, the invention mixes the substrate 10 and
the graphene oxide 20 in a specific proportion, such that the mixed
and/or entangled composite carbon material 1 has excellent
properties. More specifically, based on the total weight of the
substrate 10 and the graphene oxide 20, the graphene oxide 20
accounts for about 5 wt % to 60 wt %, 5 wt % to 40 wt %, 5 wt % to
30 wt % or 5 wt % to 20 wt %. In an embodiment, in the composite
carbon material 1, the graphene oxide 20 accounts for about 5 wt %,
10 wt %, 15 wt %, 20 wt %, 25 wt %, 30 wt %, 35 wt %, 40 wt %, 45
wt %, 50 wt %, 55 wt % or 60 wt %, or any numerical value between
any two endpoints above. When the content of the graphene oxide 20
is too low, the dispersity and flexibility of the composite carbon
material 1 are decreased. When the content of the graphene oxide 20
is too high, the electrical conductivity and hydrophilic property
of the composite carbon material 1 are decreased. Therefore, mixing
the substrate 10 and the graphene oxide 20 in a specific proportion
enables the mixed and/or entangled composite carbon material 1 to
have excellent hydrophilic property, flexibility, electrical
conductivity and dispersity, thereby achieving the unexpected
effects. The composite carbon material 1 of the invention can be
applied to conductive composite materials, flexible conductive
materials, thermally conductive materials, etc.
[0039] The substrate 10 and the graphene oxide 20 of the invention
can be uniformly dispersed/mixed because the surface of the
graphene oxide is rich in oxygen-containing functional groups, and
thus, the dispersing/mixing step is performed in a solution without
additional complicated process steps of purification. In an
embodiment, when using a one-dimensional graphene oxide such as a
graphene oxide nanoribbon (GONR), the GONR and a carbon substrate
form a uniform conductive network, enabling conductivity to
significantly increase.
[0040] Furthermore, regarding the dimension of the conducting
direction, there are at least 18 combinations of the composite
carbon material of the invention, as shown below in Table 2, but
the invention is not limited thereto.
TABLE-US-00002 TABLE 2 Combinations of composite carbon material
Composite carbon material Substrate Graphene oxide Combination 1
1-D conductor 1-D graphene oxide Combination 2 1-D conductor 2-D
graphene oxide Combination 3 2-D conductor 1-D graphene oxide
Combination 4 2-D conductor 2-D graphene oxide Combination 5 3-D
conductor 1-D graphene oxide Combination 6 3-D conductor 2-D
graphene oxide Combination 7 1-D conductor 1-D graphene oxide + 2-D
graphene oxide Combination 8 1-D conductor 1-D graphene oxide + 2-D
graphene oxide Combination 9 2-D conductor 1-D graphene oxide + 2-D
graphene oxide Combination 10 2-D conductor 1-D graphene oxide +
2-D graphene oxide Combination 11 3-D conductor 1-D graphene oxide
+ 2-D graphene oxide Combination 12 3-D conductor 1-D graphene
oxide + 2-D graphene oxide Combination 13 1-D conductor + 2-D 1-D
graphene oxide conductor Combination 14 1-D conductor + 2-D 2-D
graphene oxide conductor Combination 15 1-D conductor + 3-D 1-D
graphene oxide conductor Combination 16 1-D conductor + 3-D 2-D
graphene oxide conductor Combination 17 2-D conductor + 3-D 1-D
graphene oxide conductor Combination 18 2-D conductor + 3-D 2-D
graphene oxide conductor
[0041] FIG. 2 is a schematic diagram of a method of preparing a
composite carbon material according to an embodiment of the
invention.
[0042] Referring to FIG. 2, a substrate 10 and a graphene oxide 20
are uniformly mixed in a solvent 30, wherein the graphene oxide 20
accounts for 5 wt % to 60 wt % based on the total weight of the
substrate 10 and the graphene oxide 20. In an embodiment, the
method of preparing the graphene oxide 20 includes embedding or
inserting a nitrate, a sulfate, or a combination thereof between
layers of a carbon material or between adjacent carbon materials,
and then adding an oxidizing agent to oxidize the carbon material.
The carbon material includes a single-walled carbon nanotube, a
double-walled carbon nanotube, a multi-walled carbon nanotube, or a
graphite, and the oxidizing agent includes potassium permanganate.
In an embodiment, the solvent 30 can be deionized water. In another
embodiment, the solvent 30 can be a suitable organic solvent, such
as ethanol, acetone, N-methylpyrrolidone, the like, or a
combination thereof. It is noted that, addition of a surfactant is
not required in this mixing step, and thus, the electrical
conductivity of the composite carbon material is not reduced due to
addition of the surfactant.
[0043] Thereafter, the solvent 30 is removed. In an embodiment, a
suction filtration is performed. In another embodiment, the step of
removing the solvent 30 can be conducted by another suitable method
as needed, such as a natural drying, a baking, or the like. The
solvent 30 is removed from the mixture through a membrane filter
40. The remaining substrate 10 and graphene oxide 20 that are
uniformly mixed together form a sheet-like composite carbon
material 1 on the membrane filter 40. In an embodiment, the
membrane filter 40 can be a polyvinylidene fluoride (PVDF) filter
membrane.
[0044] Examples and Comparative Examples are provided below to
verify the effects of the composite carbon material of the
invention.
Example 1
[0045] A multi-walled carbon nanotube (MWNT) having a
one-dimensional conducting direction and a graphene oxide
nanoribbon (GONR) having a one-dimensional conducting direction
totaling 1 mg to 100 mg are uniformly dispersed in 1 ml to 50 ml of
deionized water. Then, after removing the deionized water, the
remaining MWNT and GONR that are uniformly mixed together forma
sheet-like composite carbon material, which is used to prepare a
conductive thin film of Example 1.
Comparative Example 1
[0046] The sample of Comparative Example 1 is a conventional
conductive thin film prepared with a pure multi-walled carbon
nanotube.
[0047] FIGS. 3(a), 3(c) and 3(e) are images of the conventional
conductive thin film of Comparative Example 1. FIGS. 3(b), 3(d) and
3(f) are images of the conductive thin film of Example 1 of the
invention.
[0048] After the conventional conductive thin film is bent, as
shown in FIG. 3(a), the surface thereof has many discontinued or
defective regions. However, after the conductive thin film of the
invention is bent, as shown in FIG. 3(b), the surface thereof is
still very even and uniform without any defects or damages.
[0049] FIGS. 3(c) and 3(e) are scanning electron microscope (SEM)
images of the conductive thin film prepared with the pure carbon
nanotube. After the conventional conductive thin film is bent, many
discontinued regions are produced, the film uniformity and
flexibility are significantly reduced, and the electrical
conductivity is significantly reduced.
[0050] In contrast, as shown in FIGS. 3(d) and 3(f), after the
conductive thin film prepared with the composite carbon material of
the invention is bent, the electrical conductivity remains
excellent without generation of defects or damages. In addition, as
show in FIG. 3(f), the tube-shape and ribbon-shape materials are
uniformly mixed, indicating that the graphene oxide nanoribbon and
the multi-walled carbon nanotube of the invention are uniformly
dispersed.
[0051] Furthermore, an electrical conductivity test with an LED
lamp is performed on the conventional conductive thin film of
Comparative Example 1. When the thin film is not bent, the
electrode is conducted and the LED lamp emits light, whereas when
the thin film is bent, the electrode cannot be conducted and the
LED lamp does not light up. However, when bent, the conductive thin
film of Example 1 still enables the LED lamp to emit light, forming
an electrical conduction path.
[0052] FIG. 4(a) is a resistance value distribution of the
conventional conductive thin film of Comparative Example 1. FIG.
4(b) is a resistance value distribution of the conductive thin film
of Example 1 of the invention.
[0053] Referring to FIG. 4(a), a four-point probe is used to
perform a measurement of resistance value of the conventional
conductive thin film. Due to defects or damages on the surface of
the thin film, the resistance value distribution is uneven and the
electrical conductivity is poor.
[0054] Referring to FIG. 4(b), a four-point probe is used to
perform a measurement of resistance value of the conductive thin
film of Example 1 of the invention. As shown in FIG. 4(b), the
resistance value distribution is even and stable and the electrical
conductivity is excellent.
Example 2
[0055] A multi-walled carbon nanotube having a one-dimensional
conducting direction and a graphene oxide nanoribbon (GONR) having
a one-dimensional conducting direction are mixed in different
proportions to prepare a plurality of composite carbon materials. A
sheet resistance test is then performed on the prepared composite
carbon materials.
[0056] FIG. 5 is a graph illustrating a relationship between a
resistance value and a graphene oxide content in a composite carbon
material of Example 2 of the invention.
[0057] As shown in FIG. 5, the composite carbon materials having
different electrical conductive properties can be prepared by
tuning or adjusting the content of the graphene oxide. Such
composite carbon materials having different electrical conductive
properties can be widely applied to different products. In an
embodiment, a low resistance property is desired when the composite
carbon material of the invention is applied to a conductive thin
film. In such case, the graphene oxide content is preferably within
a range of 20 wt % to 60 wt % to achieve the optimal electrical
conductive property.
Example 3
[0058] A single-walled carbon nanotube having a one-dimensional
conducting direction and a graphene oxide nanoribbon (GONR) having
a one-dimensional conducting direction are mixed in different
proportions to prepare a plurality of composite carbon materials. A
sheet resistance test is then performed on the prepared composite
carbon materials.
[0059] FIG. 6 is a graph illustrating a relationship between a
resistance value and a graphene oxide content in a composite carbon
material of Example 3 of the invention. As shown in FIG. 6, the
graphene oxide content is preferably within a range of 10 wt % to
20 wt % to achieve the optimal electrical conductive property.
Based on the results of FIGS. 5 and 6, the graphene oxide of the
invention not only enables the multi-walled carbon nanotube to be
uniformly dispersed, but also enables the single-walled carbon
nanotube to be uniformly dispersed.
Example 4
[0060] A graphene having a two-dimensional conducting direction and
a graphene oxide nanoribbon (GONR) having a one-dimensional
conducting direction are mixed in different proportions to prepare
a plurality of composite carbon materials. A sheet resistance test
is then performed on the prepared composite carbon materials.
[0061] FIG. 7 is a graph illustrating a relationship between a
resistance value and a graphene oxide content in a composite carbon
material of Example 4 of the invention. As shown in FIG. 7, the
graphene oxide content is preferably within a range of 10 wt % to
20 wt % to achieve the optimal electrical conductive property.
[0062] In view of the above, the invention can manufacture
composite carbon materials having different electrical conductive
properties by changing the type of the substrate, the content of
the substrate, the conducting dimension of the substrate and/or the
content of the graphene oxide, etc. It is appreciated by people
having ordinary skill in the art that the conducting dimension of
the graphene oxide can also be adjusted, and the invention is not
limited to the examples above.
[0063] In summary, in the invention, a graphene oxide is mixed with
a substrate (for example, a carbon-containing substrate) to form a
composite carbon material. The oxygen-containing functional groups
of the graphene oxide are beneficial to increase the dispersity
property, so the graphene oxide and the substrate cab be uniformly
dispersed in ordinary water. Furthermore, the graphene oxide itself
has electrical conductivity and can be used without requiring
further purification. In addition, the electrical conductivity of
the composite carbon material with the graphene oxide added is
better than that of the original carbon-containing substrate. In
other words, the graphene oxide of the invention can replace the
existing non-conductive surfactant that is used to uniformly
disperse the carbon substrate. By such manner, the subsequent
complicated process of purification treatment is eliminated, and
the conductive graphene oxide itself enables the electrical
conductivity of the composite carbon material to be more
excellent.
[0064] Although the invention has been described with reference to
the above embodiments, it will be apparent to those skilled in the
art that various modifications and variations can be made to the
disclosed embodiments without departing from the scope or spirit of
the invention. In view of the foregoing, it is intended that the
invention covers modifications and variations provided that they
fall within the scope of the following claims and their
equivalents.
* * * * *